全互穿网络温敏海藻酸锆凝胶球的磷吸附性能

doi:10.7503/cjcu20180064

摘要/Abstract

摘要：

制备了具有温敏性的全互穿网络聚(N-异丙基丙烯酰胺)/海藻酸锆凝胶球(PNIPAM/Alg-Zr), 探究了其吸附回收水中磷的性能. 结果发现, 吸附性能受到pH、温度和共存离子因素的影响. 酸性条件(pH=2)下可获得最大吸附量(30.42 mg/L). 低温有利于获得较高吸附量. S$O_{4}^{2-}$对吸附磷的过程有一定的干扰, 但增加S$O_{4}^{2-}$ 浓度对吸附性能的影响不大. 吸附动力学更符合准二级动力学模型, 为表面扩散和内部颗粒扩散所控制. Freundlich模型能更好地拟合等温吸附数据. 吸附磷后的PNIPAM/Alg-Zr在较高温度刺激下可获得更快的脱附速率, 并且5次循环再生后保持稳定的吸附性能. 通过零点电荷pH(pH_pzc)和X射线光电子能谱分析, 推测其吸附机理为静电吸附和配位交换. PNIPAM/Alg-Zr呈现良好的柱吸附特点, 可用Thomas模型进行模拟.

关键词: 海藻酸锆凝胶球, 全互穿网络, 温敏性, 磷, 柱吸附

Abstract:

Thermosensitive poly(N-isopropylacrylamide)/zirconium alginate hydrogel beads with full-interpenetrating network(PNIPAM/Alg-Zr) were prepared and explored as a sorbent for phosphorus(P) recovery from aqueous solutions. The sorption of P onto PNIPAM/Alg-Zr was affected by pH, temperature and co-existing anions. A maximum uptake capacity of 30.42 mg/L was observed at pH=2. A low temperature was favourable for the sorption process. The presence of S$O_{4}^{2-}$ had a certain interference on P sorption while a slight effect of S$O_{4}^{2-}$ under higher ionic strength was observed. The sorption kinetics followed the pseudo-second-order model and was regulated by surface and intraparticle diffusion. The isotherm data were well fitted to the Freundlich model. The P-loaded PNIPAM/Alg-Zr achieved a faster desorption rate under a high temperature stimulus, and the uptake capacity of P remained stable after five times regeneration. The inferred sorption mechanisms were electrostatic interaction and ligand exchange verified by the analysis of pH value at zero point charge(pH_pzc) and XPS. PNIPAM/Alg-Zr exhibited good column-sorption characteristic, and the Thomas model could fit well the experimental data.

Key words: Zirconium alginate hydrogel bead, Full-interpenetrating network, Thermosensitive, Phosphorus, Column sorption

中图分类号:

O631
O647.3

TrendMD:

骆华勇, 荣宏伟, 曾学阳, 王然登, 储昭瑞. 全互穿网络温敏海藻酸锆凝胶球的磷吸附性能. 高等学校化学学报, 2018, 39(10): 2289.

LUO Huayong,RONG Hongwei,ZENG Xueyang,WANG Randeng,CHU Zhaorui. Performance of Phosphorus Sorption on Thermosensitive Zirconium Alginate Hydrogel Beads with Full-interpenetrating Network^†. Chem. J. Chinese Universities, 2018, 39(10): 2289.

图/表 12

Fig.1 SEM images of hydrogel beads(A) Outer surface; (B) cross-section.

Fig.2 ESR of hydrogel beads at different temperatures

Fig.3 FTIR spectra of the samples before(a) and after sorption(b)

Fig.4 Effests of pH(A), species of phosphate in different pH(B), temperature(C) and co-existing anions(D) on sorption performance

Fig.5 Fitting curves of pseudo-first-order and pseudo-second-order models(A) and intraparticle diffusion model(B)P concentration/(mg·L-1): a. 25; b. 50; c. 100.

Table 1 Kinetic model parameters of P sorption

Kinetic model	Parameter	Initial P concentration/(mg·L^-1)
Kinetic model	Parameter	25	50	100
Pseudo-first-order	k₁/min^-1	4.01×10^-3	6.76×10^-3	4.13×10^-3
	q_e/(mg·g^-1)	9.95	13.79	29.28
	R²	0.991	0.927	0.961
Pseudo-second-order	k₂/(g·mg^-1·min^-1)	4.95×10^-4	6.80×10^-4	1.75×10^-4
	q_e/(mg·g^-1)	11.21	14.98	32.92
	R²	0.992	0.982	0.992
Intraparticle diffusion	k_1d/(mg·g^-1·min^0.5)	0.48	0.42	1.19
	R²	0.986	0.989	0.922
	C₁	-1.00	3.66	0.46
	k_2d/(mg·g^-1·min^0.5)	0.23	0.19	0.36
	R²	0.997	0.980	0.965
	C₂	3.06	7.70	15.94

Fig.6 Sorption equilibrium isotherms fitting with Langmuir model(A) and Freundlich model(B)Temperature/K: a. 298; b. 308; c. 318.

Table 2 Isotherm model parameters of P sorption

T/K	Langmuir			Freundlich
T/K	q_max/(mg·g^-1)	k_L/(L·mg^-1)	R²	k_F/(mg·g^-1)(L·mg^-1 $) 1 / n$	n	R²
298	39.44	0.21	0.885	12.07	3.39	0.988
308	38.53	0.16	0.920	10.73	3.30	0.984
318	36.36	0.13	0.973	9.26	3.17	0.979

Table 2 Isotherm model parameters of P sorption

T/K	Langmuir			Freundlich
T/K	q_max/(mg·g^-1)	k_L/(L·mg^-1)	R²	k_F/(mg·g^-1)(L·mg^-1 $) 1 / n$	n	R²
298	39.44	0.21	0.885	12.07	3.39	0.988
308	38.53	0.16	0.920	10.73	3.30	0.984
318	36.36	0.13	0.973	9.26	3.17	0.979

Fig.7 Effect of different temperatures on desorption(A) and reusability of hydrogel beads(B)

Fig.8 XPS spectra of hydrogel bead before(a) and after sorption(b)(A), Zr3d before P sorption(B),Zr3d after P sorption(C) and P2p of hydrogel bead after P sorption(D)

Fig.9 Breakthrough curves of P sorption

Table 3 Parameters of breakthrough curves and Thomas model for P sorption

H/cm	Q/(mL·min^-1)	c₀/(mg·L^-1)	t_b/min	t_e/min	q_total/(mg·g^-1)	k_Th/(mL·mg^-1·min^-1)	q_o/(mg·g^-1)	R²
6.5	2	50	5.0	195.0	2.65	0.55	2.97	0.938
10.0	2	50	12.0	310.0	3.54	0.31	4.11	0.961
6.5	3	50	1.5	82.0	1.52	1.02	1.62	0.921

参考文献 32

[1]	Jung K.W., Jeong T. U., Choi J. W., Ahn K. H., Lee S. H., Bioresour. Technol., 2017, 244, 23—32
[2]	Loganathan P., Vigneswaran S., Kandasamy J., Bolan N.S., Crit. Rev. Env. Sci. Tec., 2014, 44(8), 847—907
[3]	Wan J., Zhu C., Hu J., Zhang T.C., Richter-Egger D., Feng X., Zhou A., Tao T., Appl. Surf. Sci., 2017, 423, 484—491
[4]	Luo X., Wu X., Reng Z., Min X., Xiao X., Luo J., Ind. Eng. Chem. Res., 2017, 56(34), 9419—9428
[5]	Huang W., Zhang Y., Li D., J. Environ. Manage., 2017, 193, 470—482
[6]	Vasudevan S., Lakshmi J., RSC Adv., 2012, 2(12), 5234—5242
[7]	Tan W.S., Ting A. S. Y., Bioresour. Technol., 2014, 160, 115—118
[8]	Zhou Q., Lin X., Qian J., Wang J., Luo X., RSC Adv., 2015, 5(3), 2100—2112
[9]	Li X., Qi Y., Li Y., Zhang Y., He X., Wang Y., Bioresour. Technol., 2013, 142, 611—619
[10]	Wu J., Wu Z., Sun X., Yuan S., Zhang R., Lu Q., Yu Y., J. Chin. Chem. Soc., 2017, 64(2), 231—238
[11]	Dragan E. S., Chem. Eng. J., 2014, 243, 572—590
[12]	Xulu P.M., Filipcsei G., Zrínyi M., Macromolecules, 2000, 33(5), 1716—1719
[13]	Luo H., Wang Q., Tao T., Zhang T.C., Zhou A., J. Environ. Eng., 2014, 140(12), 04014044
[14]	Nguyen T.A. H., Ngo H. H., Guo W. S., Pham T. Q., Li F. M., Nguyen T. V., Bui X. T., Sci. Total. Environ., 2015, 523, 40—49
[15]	Zhang Y., Lin X., Zhou Q., Luo X., Appl. Surf. Sci., 2016, 389, 34—45
[16]	Tran H.N., You S. J., Hosseini-Bandegharaei A., Chao H. P., Water Res., 2017, 120, 88—116
[17]	Işıklan N., Küçükbalcı G., Polym. Bull., 2016, 73(5), 1321—1342
[18]	Hartanto Y., Zargar M., Wang H., Jin B., Dai S., Environ. Sci. Technol., 2016, 50(8), 4221—4228
[19]	Ju H.K., Kim S. Y., Kim S. J., Lee Y. M., J. Appl. Polym. Sci., 2002, 83(5), 1128—1139
[20]	Su Y., Cui H., Li Q., Gao S., Shang J.K., Water Res., 2013, 47(14), 5018—5026
[21]	Liu Q., Hu P., Wang J., Zhang L., Huang R., J. Taiwan Inst. Chem. E, 2016, 59, 311—319
[22]	Wu D., Gao Y., Li W., Zheng X., Chen Y., Wang Q., ACS Sustain. Chem. Eng., 2016, 4(12), 6732—6743
[23]	Acelas N.Y., Martin B. D., López D., Jefferson B., Chemosphere, 2015, 119, 1353—1360
[24]	Liu X., Zhang L., Powder Technol., 2015, 277, 112—119
[25]	Teutli-Sequeira A., Solache-Ríos M., Martínez-Miranda V., Linares-Hernández I., J. Colloid Interf. Sci., 2014, 418, 254—260
[26]	Karagöz S., Tay T., Ucar S., Erdem M., Bioresour. Technol., 2008, 99(14), 6214—6222
[27]	Liao P., Ismael Z. M., Zhang W., Yuan S., Tong M., Wang K., Bao J., Chem. Eng. J., 2012, 195, 339—346
[28]	Long F., Gong J. L., Zeng G. M., Chen L., Wang X. Y., Deng J. H., Niu Q. Y., Zhang H. Y., Zhang X. R., Chem. Eng. J., 2011, 171(2), 448—455
[29]	Sowmya A., Meenakshi S., Int. J. Biol. Macromol., 2014, 69, 336—343
[30]	Dong S., Wang Y., Water. Res., 2016, 88, 852—860
[31]	Biswas B.K., Inoue J. I., Inoue K., Ghimire K. N., Harada H., Ohto K., Kawakita H., J. Hazard. Mater., 2008, 154(1—3), 1066—1074
[32]	Jain M., Garg V.K., Kadirvelu K., Bioresour. Technol., 2013, 129, 242—248